Processes for making paper having insecticidal properties and products resulting therefrom



.Fweeoi Patented ug. 28., 1951 H2L? 5111.5 Lumina uur.:

"ffii-2,566,092 Y 'i UCTS RESULTING THEREFROM y l'1oDravvinefpplication December 7, 1946,

, v Serial No. 714,912

paper' 'having' t :APbeatingI empbs'ihofwas prepared by :melia 20 j Abenzeneernu1Siohfontaining-flO "1 ofiafpolychiorfcamphee preparea-'by @reserving 39 parts of a po1ych1ordfe'afnphenecontaining avisa,

chlorine and 39-parts off/Tween 81 (trade name for sorbitan monooleate polyoxyallylene deriva.- fntive) in ll'parte'ofberie andff'then adding 195 parts Aof water- `vvith ir'iecha'nical agitation.

i lA 32 1b.'/rearn kraft paper vias' coatedwitlithe above emulsion on aMartin'sorf'Coater. The AJ""*p'aper"was then dried 'in 'af'current of Warm-air,

Uhn: null l about 2.5 1b./ream o'f"dry'ThatraFhaVin been This paper whenwtestedfor 'tsanisectitidaracf knockdown irr5 hours andthe unheated'ipaper a 1 resin emulsion containing 10% ofafpoly- 4fchloro camphene was T`prepared. by melting* to- 35 "'gether at 65-70 C. '17 .5 parts-of Span 40 (trade name for sorbitan monopalmitate) and 17';5 parts of Tween r ('tradef'name foi sorbitari monopalmtate -polyoxy'alkylenederivative) Vyand-*then Urfacldingf'lO parts yof` the' methyl ester of hydro- 40 genated rosin and nally 50 parts of ai-:poly- --`chloro camphene-containing 67.8%l off: chlorine. YWhen" themxturemwas' homogeneous', 265 parts of water at'thesame'temperature of `65u70 C. were 'added withA mechanical agitation. A 32 1b;/ream kraft paper was coatediwith'the 'f'fabove emulsion'v on 'a MartinsonCoater aitv'l'the *"'ratel of l--lbi/re'amfand of 15 lbg/reamz'fffrfThe M4fpaper was then dried in-a vcurrent vof fwarm air and tested for its insecticidal activity. -sThe 10 aofflbs/eain-'coated paper had a 1'00%-kn'ockdwn in /6'hours` 'and the A15'. lb/ram boated'papehad a knockdown in 5 hourswhereasf'thercontrol had no knockdown in 0 hours. Both of the coated papers had a 24'ho'1ir"kil1 'of 100% compared to 5th-et 24^ihoirkii1ief13-2% -forthei control;

Emample V A clay coating color was prepared by mixing 100 parts of clay, 152 parts of Water, 14 parts of casein, and 2 parts of soda ash. To this coating color was added 100 parts of a benzene .emulsion of a polychloro camphene containing 67.8%

III

Martinson Coater. a current of warm air it was tested for insec-` ticidal activity against house flies and was" found chlorine and prepared as described in Example` A 32 lb./ream kraft paper was coated atl the rate of 20 lb./ream of this coating color,v using .a

After drying the paper; in

taining 10% polychloro camphene and prepared as described in Example III were added to 1920 parts of a 2.6% bleached sulte pulp to form a furnish containing 5% polychloro camphene based on the weight of dry pulp. After adding 1.5%i dry resin size in a 3% emulsion and suicient alum to adjust the pH to 4.4-4.6, the sized Y `pulp was run out and made into handsheets. When tested for its insecticidal activity this paper had a: 24-hour kill of 100% against house flies Y as compared with' a 3.2% kill for the control.

to have a :Z4-hour kill of 100% compared to 3.2%

for the control.

Example VI A lacquer containing a polychloro camphene,

` The polychloro bicyclic terpenes, used in ac- .cordance with this invention in the preparation of paper having insecticidal properties, are prepared'by chlorinating a bicyclic terpene until the terpene contains from about 40% to about 75% chlorine and preferably from about 60% to about 72% chlorine. Polychloro bicyclic terpenes convhaving a chlorine content of 67.8%, was pre# a A 32 lb./rean`1 kraft paper Was coated with this lacquer at the rate of 7 lb./ream on a Martinson Coater and then dried in a current of warm air. When tested for its insecticidal activity, this paper had a 24-hour killof` 100% compared to the 3.2 kill for the control.

Example VII A wax emulsion containing a polychloro camphene, having a chlorine content of 67.8%, was prepared by adding 80 parts of the polychloro camphene to 1920 parts of a commercial aqueous crudel scale wax emulsion (an amount equivalent toabout 320 partsof wax). 1

A 32 lb./ream kraft paper was coated with this wax emulsion at the rate `of 4 lbs. of solids per ream on a Martinson Coater. The paper was then dried in a current of warm air and when tested for its insecticidal activity was found to have a 24-hour kill of 100% compared to a 3.2% kill for the control.

Example ivm A polychloro camphene containing 67.8% chlorine was deposited on diatomaceous silica by dispersing partsl of the silica in 75 parts of a 6.7% solution of the polychloro-camphene in benzene. The benzenewas then evaporated and the silica was ground to pass through a 10G-meshv screen. The-polychloro'carnphene content of this powder was 20%.

To a paper furnish containing 2.6% bleached sulte pulp (1920 parts) was added 12.5 parts of the above diatomaceous silica-polychloro cam-A phene powder. After adding 1.5% dry rosin size in a-3% emulsion and sufficient alum in a 12% solution t0 adjustto pH to 4.4-4.6, the sized pulp was run out and made into handsheets. The paper so prepared'contained 5% polychloro terpene by weight.

This paper was tested for its insecticidal acftivity and found to have a 24-hour kill of 100% against house es. Y

Erdmplre IX v Twenty-five parts of albenzene emulsion con-f vtaining less than 40% chlorine are not sufficiently active to impart insecticidal properties to paper. The same thing istrue for polychloro bicyclic terpenes containing more than 75% chlorine.

Polychloro bicyclic terpenes which may be used to impart insecticidal properties to paper are` polychloro camphenes prepared by chlorinating camphene, camphene hydrochloride and isocamphene; polychloro pinanes prepared by chlorinating pinane and pinene hydrochloride; polychloro camphenes which are prepared by chlo-VV rinating such compounds as camphene, pinene,Vv

bornyl chloride and isobornyl chloride; and chlo-v rinated fenchenes.

s The polychloro bicyclic terpenes may be in-l corporated into paper or board, in order to impart insecticidal properties to the paper or board,

by treating the paper or paper fiber with theY polychloro bicyclic terpene by any convenient method which will leave a deposit of the polychloro terpene on the fiber material making up the'paper or in the paper or on its surface.

A convenient method of incorporating a poly-1' chloro bicyclic terpene in paper is to add the toxicant, in the form of a dispersible powder, a

coating composition which contains the toxicant.

Any type of coating composition'may be used for this purpose.' For example, the polychloro'.

bicyclic terpene may be added to wax and the paper dipped or coated by any means with the molten wax composition. The polychloro bicyclic' terpene may also be added to a Vvpaint such as a lacquer, a clay coating color, etc., used in the decoration of paper -lfor wallpaper, etc; toxicant may also be applied as a coating in'Tthe form of an emulsion such as a resin emulsion, an organic solvent emulsion or a wax emulsion, which contains the polychloro terpene. Any means of applying the coating composition may befused as by a coating machine, a simple painting operation, etc. Y

' The polychloro bicyclic Vterpene may also be dissolved in an organic solvent such as benzene. toluene, xylene, gasoline, carbon tetrachloride, chloroform, alcohol, etc., and applied to paper by immersing in or passing the paper through the solution' and evaporating the solvent from the paper. i

Paper or board which has been treated with a polychloro bicyclic terpene, as by adding the toxioant to the furnish or by coating the paper or board with a composition containing the toxicant, has a very high degree of insecticidal activity. As little as 1% by weight of the paper of the polychloro bicyclic terpene is su'icient to give an excellent kill when insects are in contact with the paper. Usually from about 3% to is a practical amount to be used to attain the desired activity. However, more may be used if desired for specific purposes. This nsecticidal activity of the paper is a prolonged action and retains its activity even after many months of exposure under normal conditions.

Paper and board into which a polychloro bicyclic terpene has been incorporated is useful as wallpaper, permanent record paper, wrapping and bag paper, lining paper, insulating-bat wrapping, and for making storage bags, closets and cartons.

What I claim and desire toprotect by Letters Patent is:

1. In a process for the manufacture of paper having insecticidal properties, the step which comprises coating paper with a composition containing a chlorinated bicyclic terpene containing from about 40% to about 75% chlorine, the amount of said terpene present in the coated paper being at least 1% by weight of the paper, whereby the paper is rendered toxic to insects.

2. In a process for the manufacture of paper having insecticidal properties, the step comprising the addition of a chlorinated bicyclic terpene, containing from about 40% to about 75% chlorine, to the paper furnish in the amount of at least 1% by weight of the paper fibers, whereby the paper is rendered toxic to insects.

3. A paper having insecticidal properties comprising a fibrous paper having incorporated therewith a chlorinated bicyclic terpene containing from about 40% to about 75% chlorine, the amount of said terpene present being at least 1% by weight of the paper, whereby the paper is toxic to insects.

4'. A paper as in claim 3 in which the chlorinated bicyclic terpene is incorporated with the paper as a coating thereon.

5. A paper as in claim 3 in which the chlorinated bicyclic terpene is substantially uniformly distributed throughout the paper.

6. A paper having insecticidal properties comprising a fibrous paper having incorporated therewith a chlorinated camphene containing from about to about 72% chlorine, the amount of said camphene present being at least 1% by Weight of the paper, whereby the paper is toxic to insects.

7. In a process for the manufacture of paper having insecticidal properties, the step comprising the incorporation of a chlorinated bicyclic terpene containing from about 40% to about 75% chlorine with the ber, the amount of said terpene present being at least 1% by weight of the paper, whereby the paper is toxic to insects.

PAUL MAYFIELD.

REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PATENTS Number Name Date 1,366,106 Weeks Jan. 18, 1921 2,030,653 Quinn Feb. 11, 1936 2,071,822 Ellis Feb. 23, 1937 2,143,043 Wexler Jan. 10, 1939 2,185,954 Ryner Jan. 2, 1940 2,488,590 Evans et al. ---1---- Nov. 22, 1949 FOREIGN PATENTS Number Country Date 4,558 Great Britain 1889 624,176 Great Britain May 30, 1949 OTHER REFERENCES Cotton et al.: Journal of Economic Entomology, vol. 37, No. 1, page 140, February 1944.

Journal Textile Institute, October 1944, page O. S. R. D. Committee on Medical Research Report No. 26, Sec. 1, October 31, 1945, page 5, 

7. IN A PROCESS FOR THE MANUFACTURE OF PAPER HAVING INSECTICIDAL PROPERTIES, THE STEP COMPRISING THE INCORPORATION OF A CHLORINATED BICYCLI TERPENE CONTAINING FROM ABOUT 40% TO ABOUT 75% CHLORINE WITH THE FIBER, THE AMOUNT OF SAID TERPENE PRESENT BEING AT LEAST 1% BY WEIGHT OF THE PAPER, WHEREBY THE PAPER IS TOXIC TO INSECTS. 